Nonlinear optical devices formed from poled polymer structures are used in numerous applications, such as planar waveguide modulators or second harmonic generators in integrated circuits. Typically the poled polymer structure is fabricated by poling a polymer film after the film has been formed. For example, a polymer film containing chromophores with high polarizabilities can be heated to near its glass transition temperature and subjected to an electrostatic field (poled power supply) to align the chromophores based upon their dipole moments. When the polymer film is cooled, the molecules are frozen in the oriented (poled) position. While this is a straightforward process, there are disadvantages. One significant disadvantage is the gradual relaxation of the oriented position over time, and hence, instability in the nonlinear characteristics of the film. Another disadvantage is the multi-step process of: forming the polymer structure; thermal cycling the structure to near glass transition temperature; applying a relatively large electrostatic poling field to the structure; and bringing the polymer structure back to room temperature. Therefore there is the need for a poled polymer structure that can be formed in a single stage process while exhibiting an extended temporal stability.